Compositions containing 1,1-di-substituted alkene compounds for preparing polymers having enhanced glass transition temperatures

ABSTRACT

The disclosure relates to compositions containing 1,1-disubstituted alkene compounds capable of preparing polymers having glass transition temperatures above room temperature. The present teaching also relates to polymers prepared 1,1-disubstituted alkene compounds which exhibit glass transition temperatures of 60° C. The disclosure also relate to methods for enhancing the glass transition temperatures of polymers prepared from 1,1-disubstituted alkene compounds.

FIELD

Disclosed are compositions containing 1,1-disubstituted alkene compoundsfor preparing polymers having enhanced glass transition temperatures,polymeric compositions prepared from such compositions and methods ofenhancing the glass transition temperatures of polymers prepared from1,1-disubstituted alkene compounds.

BACKGROUND

1,1-disubstituted alkene compounds find use in a number of applicationssuch as adhesives, coatings, composites and the like. 1,1-disubstitutedalkene compounds, with two ester substituents on the alkene double bond,are commonly known as methylene malonates. These compounds have beenknown since the 19^(th) century and in the mid-20^(th) century a numberof researchers worked with these compounds, see D'Alelio U.S. Pat. No.2,330,033; Coover U.S. Pat. No. 3,221,745 and U.S. Pat. No. 3,523,097;Halpern U.S. Pat. No. 3,197,318; and Ponticello U.S. Pat. No. 4,056,543and U.S. Pat. No. 4,160,864, all incorporated herein by reference intheir entirety for all purposes. Despite this work the 1,1-disubstitutedalkene compounds have not been commercialized. The disclosed processesfor the preparation of these compounds produce a number of by-productsthat negatively impact the stability of the desired products whichprecludes the reasonable use of the compounds. In addition, some of theby-products and starting materials are difficult to separate from thedesired compounds. 1,1-disubstituted alkene compounds polymerize rapidlyat room temperature under mild conditions in presence of nucleophilic orbasic initiating species, which render them both useful, as well as,present problems with their stability. The problems with the processesand the products of the processes were not fully appreciated untilMalofsky et al. studied the compounds and processes and developed waysto produce these compounds without the presence of starting materialsand by-products that negatively impact their stability. Malofsky et. al.developed methods for enhancing the stability of such compounds whilefacilitating cure of the compounds at room temperature upon demand, seeMalofsky et al. U.S. Pat. No. 8,609,885; U.S. Pat. No. 8,884,405;US2014/0329980; and US 2015/0073110; all incorporated herein byreference in their entirety for all purposes.

The work of Malofsky et al. resulted in commercial interest in1,1-disubstituted alkene compounds for use in a variety of applications.For many uses the 1,1-disubstituted alkene compounds prepared in theMalofsky et al. patents and applications provide advantageousproperties. Many of the 1,1-disubstituted alkene compounds prepared inthe Malofsky et al. patents and applications exhibit glass transitiontemperatures near or below room temperature. Although the low glasstransition temperatures are advantageous for a number of applications,to broaden the application scope for these compounds it is desirable todevelop 1,1-disubstituted alkene compounds and compositions that canprepare polymers with higher glass transition temperatures.

Thus, what is needed are 1,1-disubstituted alkene compounds that arecapable of forming polymers with glass transition temperatures of 60°C., more preferably above 80° C., even more preferably above 100° C. andeven more preferably above 120° C. What are also needed are methods forenhancing the glass transition temperatures of polymers prepared from1,1-disubstituted alkene compounds.

SUMMARY

The disclosure relates to compositions containing 1,1-disubstitutedalkene compounds capable of preparing polymers having glass transitiontemperatures above room temperature. The present teaching also relatesto polymers prepared from 1,1-disubstituted alkene compounds whichexhibit glass transition temperatures above room temperature. Thedisclosure also relates to methods for enhancing the glass transitiontemperatures of polymers prepared from 1,1-disubstituted alkenecompounds. Disclosed herein are compositions comprising one or morefirst 1,1-disubstituted alkene compounds having two carbonyls bonded tothe 1 carbon atom wherein each carbonyl group independently has ahydrocarbyl group bonded to the carbonyl groups through a direct bond ora heteroatom wherein the one or more first 1,1-disubstituted alkenecompounds have one or more of the hydrocarbyl groups comprising an arylgroup, aralkyl group, alkaryl group with the aryl group bonded to the 1carbon atom, a cycloalkyl group, an alkyl group with a cycloalkyl groupon the 1 carbon atom, or a branched alkyl group wherein the 1 carbonatom is a tertiary or the 1 and 2 carbon atoms are secondary wherein thecomposition is polymerizable and contains a sufficient amount of thefirst 1,1-disubstituted alkene compounds such that a polymer preparedfrom the composition exhibits a glass transition (Tg) temperature ofgreater than 35° C. In some embodiments the compositions furthercomprise one or more second 1,1-disubstituted alkene compounds whereinthe hydrocarbyl groups prepare homopolymers having a glass transitiontemperature of less than 60° C. In some embodiments the one or moresecond 1,1-disubstituted alkene compounds contain hydrocarbyl groupswhich prepare homopolymers having a glass transition temperature about30 to less than 60° C. or less. In some embodiments the compositionprepares polymers with a Tg of 60° C. or greater. In some embodimentsthe compositions contain 10 percent by weight or greater of the first1,1-disubstituted alkene compounds. 1,1-disubstituted alkene compoundsare compounds wherein a central carbon atom is doubly bonded to anothercarbon atom to form an alkylene group, for example an ethylene group.The central carbon atom is further bonded to two carbonyl groups. Eachcarbonyl group is bonded to a hydrocarbyl group through a direct bond orhetero atom. With respect to the hydrocarbyl groups bonded to thecarbonyl groups the 1 carbon atom refers to the carbon atom bonded tothe carbonyl group through a direct bond or hetero atom. With respect tothe hydrocarbyl groups bonded to the carbonyl groups the number of thecarbon atom (for instance 2 or 3) refers to the number of the carbonatom from the direct bond or a heteroatom bonded to the carbonyl group.In some embodiments disclosed is a composition comprising about 10weight percent or greater of one or more first 1,1-disubstituted alkenecompounds wherein each carbonyl group independently has a hydrocarbylgroup bonded to the carbonyl groups by a direct bond, an oxygen atom, anitrogen atom or a sulfur atom wherein one or more of the hydrocarbylgroups comprise an aryl group, aralkyl group, alkaryl group with thearyl group bonded to the 1 or 2 carbon atom, a cycloalkyl group, analkyl group with a cycloalkyl group on the 1 or 2 carbon atom, or abranched alkyl group wherein the 1 carbon atom is a tertiary or the 1and 2 carbon atoms are secondary; and about 10 weight percent or greaterof one or more second 1,1-disubstituted alkene compounds wherein eachcarbonyl group independently has a hydrocarbyl group bonded to thecarbonyl groups by a direct bond, an oxygen atom, a nitrogen atom or asulfur atom and the hydrocarbyl groups are selected such thathomopolymers prepared from the second 1,1-disubstituted alkenes exhibitglass transition temperatures of less than 60° C.

Such compounds are illustrated by the formula 1 or 2:

wherein: R¹ is separately in each occurrence a hydrocarbyl groupcomprising an aryl group, aralkyl group, alkaryl group with the arylgroup bonded to the 1 carbon atom, a cycloalkyl group, an alkyl groupwith a cycloalkyl group on the 1 carbon atom, or a branched alkyl groupwherein the 1 carbon atom is a tertiary or the 1 and 2 carbon atoms aresecondary; R² is, separately in each occurrence a hydrocarbyl groupwherein a homopolymer prepared therefrorm exhibits a Tg of less than 60°C.; R′ is separately in each occurrence hydrocarbyl or hydrogen and X isa heteroatom or a direct bond. The remainder of the one or more1,1-disubstituted alkene compounds can be one or more of any other1,1-disubstituted alkene compounds.

In some embodiments the remainder of the one or more 1,1-disubstitutedalkene compounds contain hydrocarbyl groups, which correspond to R¹,which comprise straight or branched chained alkyl groups having onesecondary carbon atom or a tertiary carbon atom not directly connectedto the carbonyl carbon or to a heteroatom connected to a carbonyl carbonatom, examples of such other compounds include those corresponding toformula 3.

Such compositions may further include one or more compounds containingthe core unit of two or more 1,1-disubstituted alkene compounds whereinone of the carbonyl groups of each compound is bonded through oxygenatoms to a polyvalent hydrocarbyl group, wherein the composition iscrosslinked when polymerized. Such compounds can be represented byformula 4:

wherein, R′, R¹, R² and X are as described hereinbefore; R³ isseparately in each occurrence a polyvalent hydrocarbon group; a isseparately in each occurrence an integer of 1 or more; b is separatelyin each occurrence an integer of 0 or more wherein the sum of a and b is2 or greater and the number of valences of R³ is equal to the sum of aand b.

In some embodiments the composition comprises one or more first1,1-disubstituted alkene compounds having at least two hydrocarbylgroups. Such compounds have at least one hydrocarbyl group which is anaryl group, aralkyl group, alkaryl group with the aryl group bonded tothe 1 or 2 carbon atom, a cycloalkyl group, an alkyl group with acycloalkyl group on the 1 or 2 carbon atom, or a branched alkyl groupwherein the 1 carbon atom is a tertiary or the 1 and 2 carbon atoms aresecondary. Such compounds further have least one hydrocarbyl group whichis alkyl with a primary 1 carbon atom or a secondary 1 carbon atom and aprimary 2 carbon atom, alkenyl with a primary 1 carbon atom or asecondary 1 carbon atom and a primary 2 carbon atom, alkaryl wherein thearyl group is bonded to a carbon atom which is 3 or more carbon atomsfrom the direct bond, or heteroatom, alkyl group with a cycloalkyl groupbonded to a carbon atom which is 3 or more carbon atoms from the directbond, or heteroatom, or a polyalkylene ether. In some embodimentsdisclosed are compositions wherein the one or more first1,1-disubstituted alkene compounds have at least one hydrocarbyl groupwhich is an aryl group, aralkyl group, alkaryl group with the aryl groupbonded to the 1 or 2 carbon atom, a cycloalkyl group, an alkyl groupwith a cycloalkyl group on the 1 or 2 carbon atom, or a branched alkylgroup wherein the 1 carbon atom is a tertiary or the 1 and 2 carbonatoms are secondary and at least one hydrocarbyl group which is C₁₋₈alkyl with a primary 1 carbon atom or a secondary 1 carbon atom and aprimary 2 carbon atom.

In some embodiments the composition comprises about 10 mole percent ormore of one or more first 1,1-disubstituted alkene compounds wherein theTg of the copolymers prepared therefrom is 60° C. or greater. In someembodiments the composition comprises about 25 mole percent by weight ormore of the one or more of the first 1,1-disubstituted alkene compoundswherein the Tg of the copolymers prepared therefrom is 80° C. orgreater. In some embodiments the composition comprises about 45 molepercent or more of the one or more first 1,1-disubstituted alkenecompounds wherein the Tg of the copolymers prepared therefrom is 100° C.or greater. In some embodiments the composition comprises about 65 molepercent or more of the one or more first 1,1-disubstituted alkenecompounds wherein the Tg of the copolymers prepared therefrom is 120° C.or greater.

In some embodiments the compositions comprise one or more first1,1-disubstituted alkene compounds and one or more second1,1-disubstituted alkene compounds which exhibit a purity of 95 molepercent or greater, have one mole percent or less of the analogous1,1-disubstituted alkane, 1 mole percent or less of an impuritycontaining a dioxane group, about 1 mole percent of less of any impurityhaving the alkene group replaced by an analogous hydroxyalkyl groupwherein mole percent is based on the total moles in the1,1-disubstituted alkene compound.

In some embodiments disclosed are compositions wherein copolymersprepared from the composition exhibit a glass transition temperaturedetermined according to the formula:

Tg=Y*W+V±15° wherein

Y is the mole percent of the first 1,1-disubstituted alkene compound;W is the Tg of the first 1,1-disubstituted alkene compound minus the Tgof the second 1,1-disubstituted alkene compound: andV is the Tg of the second 1,1-disubstituted alkene compound;wherein Tg is expressed in ° C.

Disclosed herein are polymers prepared from any of the monomercompositions disclosed herein, for instance from one or more first1,1-disubstituted alkene compounds. Disclosed are copolymers preparedfrom one or more first 1,1-disubstituted alkene compounds and one ormore second 1,1-disubstituted alkene compounds. The disclosure furtherrelates to polymers prepared from about 10 weight percent or greater ofone or more first 1,1-disubstituted alkene compounds wherein eachcarbonyl group independently has a hydrocarbyl group bonded to thecarbonyl groups by a direct bond, an oxygen atom, nitrogen atom or asulfur atom wherein one or more of the hydrocarbyl groups comprising anaryl group, aralkyl group, alkaryl group with the aryl group bonded tothe 1 or 2 carbon atom, a cycloalkyl group, an alkyl group with acycloalkyl group on the 1 or 2 carbon atom, or a branched alkyl groupwherein the 1 carbon atom is a tertiary or the 1 and 2 carbon atoms aresecondary; and about 10 weight percent or greater of one or more second1,1-disubstituted alkene compounds wherein each carbonyl groupindependently has a hydrocarbyl group bonded to the carbonyl groups by adirect bond, or a heteroatom and the hydrocarbyl groups are selectedsuch that homopolymers prepared from the second 1,1-disubstitutedalkenes exhibit glass transition temperatures of less than 60° C. Thepolymer may include one or more compounds containing two or more coreunits of 1,1-disubstituted alkene compounds wherein one of the carbonylgroups of each compound is bonded through oxygen atoms to a polyvalenthydrocarbyl group, wherein the polymer is crosslinked. Disclosed arecopolymers wherein the second 1,1-disubstituted alkenes have hydrocarbylgroups which are alkyl with a primary 1 carbon atom or a secondary 1carbon atom and a primary 2 carbon atom, alkenyl with a primary 1 carbonatom or a secondary 1 carbon atom and a primary 2 carbon atom, alkarylwherein the aryl group is bonded to a carbon atom which is 3 or morecarbon atoms from the direct bond or heteroatom, alkyl group with acycloalkyl group bonded to a carbon atom which is 3 or more carbon atomsfrom the direct bond or heteroatom, or a polyalkylene ether.

In some embodiments, disclosed are polymers which comprise 100 molepercent by weight of one or more of the first 1,1-disubstituted alkenecompounds wherein at least one of the hydrocarbyl groups comprisefenchyl, menthyl, isobornyl, furfuryl, phenethyl, or adamantyl groupswherein the polymer exhibits a glass transition temperature of 120° C.or greater. In some embodiments, the polymers include the one or morefirst 1,1-disubstituted alkene compounds which have only one of thehydrocarbyl groups comprising an aryl group, aralkyl group, alkarylgroup with the aryl group bonded to the 1 carbon atom, a cycloalkylgroup, an alkyl group with a cycloalkyl group on the 1 carbon atom, or abranched alkyl group wherein the 1 carbon atom is a tertiary or the 1and 2 carbon atoms are secondary and at least one other hydrocarbylgroup is alkyl with a primary 1 carbon atom or a secondary 1 carbon atomand a primary 2 carbon atom, alkenyl with a primary 1 carbon atom or asecondary 1 carbon atom and a primary 2 carbon atom, alkaryl wherein thearyl group is bonded to a carbon atom which is 3 or more carbon atomsfrom the direct bond or heteroatom, alkyl group with a cycloalkyl groupbonded to a carbon atom which is 3 or more carbon atoms from the directbond or heteroatom, or a polyalkylene ether. These polymers are preparedfrom compounds represented by Formula 1 and include all embodiments ofR¹, R², R′ and X.

In another embodiment, disclosed is a method comprising contacting oneor more first 1,1-disubstituted alkene compounds with one or more second1,1-disubstituted alkene compounds with a polymerization initiator underconditions to polymerize the composition and the glass transitiontemperature of the resulting polymer is increased over the glasstransition temperature of a homopolymer of the one or more second1,1-disubstituted alkene compounds. In some embodiments about 10 molepercent or greater of one or more first 1,1-disubstituted alkenecompounds is present in the compounds contacted.

In some embodiments the invention is a composition comprising one ormore first 1,1-disubstituted alkene compounds wherein each carbonylgroup independently has a hydrocarbyl group bonded to the carbonylgroups by a direct bond or a heteroatom wherein one or more of thehydrocarbyl groups comprise a menthyl, fenchyl, isobornyl, furfuryl,phenethyl, 2-phenyl propyl or adamantyl.

The compositions disclosed are capable of preparing polymers based on1,1-disubstituted alkene compounds having glass transition temperaturesof greater than room temperature, some compositions prepare polymershaving glass transition temperatures of about 60° C. or greater, somecompositions prepare polymers having glass transition temperatures ofabout 80° C. or greater, some compositions prepare polymers having glasstransition temperatures of about 100° C. or greater and somecompositions prepare polymers having glass transition temperatures ofabout 120° C. or greater. The polymers disclosed herein exhibit glasstransition temperatures of about 60° C. or greater, some polymersexhibit glass transition temperatures of about 80° C. or greater, somepolymers exhibit glass transition temperatures of about 100° C. orgreater and some polymers exhibit glass transition temperatures of about120° C. or greater. The methods disclosed facilitate preparation of1,1-disubstituted alkene compound based compositions that can deliverpolymers having desired or targeted glass transition temperatures. Themethods disclosed allow the tailoring of polymers of 1,1-disubstitutedalkene compounds to have desired or targeted glass transitiontemperatures. The compositions and methods of the invention facilitatethe use of 1,1-disubstituted alkene compounds in a broader variety ofapplications, for instance adhesives and coatings where greaterstructural rigidity and modulus are desired, components for opticalfibers, resins and other adhesive and coating applications whereexposure to high temperature is expected, and the like.

DESCRIPTION OF THE DRAWINGS

FIG. 1 is a DSC trace of the polymer based on fenchyl ethyl methylenemalonate.

FIG. 2 is a TGA trace of fenchyl ethyl methylene malonate.

FIG. 3 is a DSC trace of the polymer based on phenyl propyl ethylmethylene malonate (PEMM).

FIG. 4 is a TGA trace of the polymer based on phenyl propyl ethylmethylene malonate (PEMM).

FIG. 5 is a DSC trace of the polymer based on ethyl 2-benzoylacrylate(EBA ketoester).

FIG. 6 is a DSC trace of the copolymers of DEMM and F3M in variousratios demonstrating that the Tg can be adjusted by varying the ratiosof monomers.

DETAILED DESCRIPTION

The explanations and illustrations presented herein are intended toacquaint others skilled in the art with the disclosure, its principles,and its practical application. The specific embodiments of the presentdisclosure as set forth are not intended as being exhaustive or limitingof the disclosure. The scope of the disclosure should be determined withreference to the appended claims, along with the full scope ofequivalents to which such claims are entitled. The disclosures of allarticles and references, including patent applications and publications,are incorporated by reference for all purposes. Other combinations arealso possible as will be gleaned from the following claims, which arealso hereby incorporated by reference into this written description.

The disclosure relates to a curable composition, which can be cured ondemand at ambient conditions using one or more first 1,1-disubstitutedalkene compounds. In general the disclosed compositions contain1,1-disubstituted alkene compounds having two carbonyl groups on the 1carbon atom wherein hydrocarbyl groups are bonded to a portion of thecarbonyl groups so as to enhance the glass transition temperature ofpolymers containing such first 1,1-disubstituted alkene compounds. Inthis context the 1 carbon atom refers to the carbon of the alkene groupbonded to carbonyl groups, alkene 1 carbon atom. The first1,1-disubstituted alkene compounds may have one or more of thehydrocarbyl groups bonded to the carbonyl groups, which enhance theglass transition temperature of polymers containing the first1,1-disubstituted alkene compounds. In essence a sufficient amount ofsuch compounds are contained in compositions containing the first1,1-disubstituted alkene compounds to result in polymers having desiredor targeted glass transition temperatures of 60° C. or greater.

1,1-disubstituted alkene compounds are compounds wherein a centralcarbon atom is doubly bonded to another carbon atom to form an alkylenegroup, for example an ethylene group. The central carbon atom is furtherbonded to two carbonyl groups. Each carbonyl group is bonded to ahydrocarbyl group through a direct bond or a heteroatom. Where thehydrocarbyl group is bonded to the carbonyl group through a direct bond,a keto group is formed. Where the hydrocarbyl group is bonded to thecarbonyl group through a heteroatom an ester, amide or thioester isformed, in a preferred embodiment the hydrocarbyl group is bonded to thecarbonyl group through an oxygen atom, such that an ester group isformed. The 1,1-disubstituted alkene compounds useful herein may haveall ester, amide or thioester groups, all keto groups or a mixturethereof. Compounds with all ester groups are preferred due to theflexibility of synthesizing a variety of such compounds.

One or more as used herein means that at least one, or more than one, ofthe recited components may be used as disclosed. Residual content of acomponent refers to the amount of the component present in free form orreacted with another material, such as a polymer. Typically, theresidual content of a component can be calculated from the ingredientsutilized to prepare the component or composition. Alternatively, it canbe determined utilizing known analytical techniques. Heteroatom as usedherein means nitrogen, oxygen, and sulfur, more preferred heteroatomsinclude nitrogen and oxygen with oxygen most preferred. Hydrocarbyl asused herein refers to a group containing one or more carbon atombackbones and hydrogen atoms, which may optionally contain one or moreheteroatoms. Where the hydrocarbyl group contains heteroatoms, theheteroatoms may form one or more functional groups well known to oneskilled in the art. Hydrocarbyl groups may contain cycloaliphatic,aliphatic, aromatic or any combination of such segments. The aliphaticsegments can be straight or branched. The aliphatic and cycloaliphaticsegments may include one or more double and/or triple bonds. Included inhydrocarbyl groups are alkyl, alkenyl, alkynyl, aryl, cycloalkyl,cycloalkenyl, alkaryl and aralkyl groups. Cycloaliphatic groups maycontain both cyclic portions and noncyclic portions. Hydrocarbylenemeans a hydrocarbyl group or any of the described subsets having morethan one valence, such as alkylene, alkenylene, alkynylene, arylene,cycloalkylene, cycloalkenylene, alkarylene and aralkylene. Valence asused herein means a covalent bond between a hydrocarbyl orhydrocarbylene group and another group such as a carbonyl, oxygen,nitrogen or sulfur group or atom. As used herein percent by weight orparts by weight refer to, or are based on, the weight of thecompositions unless otherwise specified.

Unless defined otherwise, all technical and scientific terms used hereinhave the meaning commonly understood by a person skilled in the art towhich this disclosure belongs. The following references provide one ofskill with a general definition of many of the terms used in thisdisclosure: Singleton et al., Dictionary of Microbiology and MolecularBiology (2nd ed. 1994); The Cambridge Dictionary of Science andTechnology (Walker ed., 1988); The Glossary of Genetics, 5th Ed., R.Rieger et al. (eds.), Springer Verlag (1991); and Hale & Marham, TheHarper Collins Dictionary of Biology (1991). As used herein, thefollowing terms have the meanings ascribed to them below, unlessspecified otherwise.

A preferred class of 1,1-disubstituted alkene compounds are themethylene malonates which refer to compounds having the core unitrepresented by Formula 4:

The term “monofunctional” refers to 1,1-substituted alkene compounds ormethylene malonates having only one core unit. The term “difunctional”refers to 1,1-disubstituted alkene compounds or a methylene malonateshaving two core units bound through a hydrocarbylene linkage between oneoxygen atom on each of two core units. The term “multifunctional” refersto refers to 1,1-disubstituted alkene compounds or methylene malonateshaving more than one core units which form a chain through ahydrocarbylene linkage between one oxygen atom on each of two adjacentcore units. The terms “latent acid-forming impurities” or “latentacid-forming impurity” refer to any impurity that, if present along withthe recovered 1,1-disubstituted alkene compounds or methylene malonates,will with time be converted to an acid. The acid formed from theseimpurities tends to result in overstabilization of the 1,1-disubstitutedalkene compounds, thereby reducing the overall quality and reactivity ofthe compounds. The term “ketal” refers to molecule having a ketalfunctionality; i.e. a molecule containing a carbon bonded to two —ORgroups, where O is oxygen and R represents any hydrocarbyl group, forexample an alkyl group. As used herein, the term “stabilized,” e.g., inthe context of “stabilized” 1,1-disubstituted alkene compounds orcompositions comprising same, refers to the tendency of the compounds(or their compositions) to substantially not polymerize with time, tosubstantially not harden, form a gel, thicken, or otherwise increase inviscosity with time, and/or to substantially show minimal loss in curespeed (i.e., cure speed is maintained) with time. As used herein, theterm “shelf-life,” e.g., as in the context of 1,1-disubstituted alkenecompounds having an improved “shelf-life,” refers to the1,1-disubstituted alkene compounds which are stabilized for a givenperiod of time, e.g., 1 month, 6 months, or even 1 year or more.

Exemplary hydrocarbyl groups comprise straight or branched chain alkyl,straight or branched chain alkenyl, straight or branched chain alkynyl,cycloalkyl, alkyl substituted cycloalkyl, aryl, aralkyl, alkaryl,wherein the hydrocarbyl groups may contain one or more heteroatoms inthe backbone of the hydrocarbyl group and may be substituted with asubstituent that does not negatively impact the ultimate function of thecompounds or polymers prepared from the compounds. Exemplarysubstituents include alkyl, halo, alkoxy, alkylthio, hydroxyl, nitro,cyano, azido, carboxy, acyloxy, and sulfonyl groups; more preferredsubstituents include alkyl, halo, alkoxy, alkylthio, and hydroxylgroups, and halo, alkyl and alkoxy are even more preferred. Alkarylmeans an alkyl group with an aryl group bonded thereto. Aralkyl means anaryl group with an alkyl group bonded thereto and include alkylenebridged aryl groups such as diphenyl methylene or propylene groups. Arylincludes groups containing more than one aromatic ring. Cycloalkylincludes groups containing one or more rings including bridged rings.Alkyl substituted cycloalkyl means a cycloalkyl group having one or morealkyl groups bonded to the cycloalkyl ring. Exemplary hydrocarbyl groupsare C₁₋₂₀ hydrocarbyl groups. Exemplary hydrocarbyl groups withheteroatoms in the backbone are alkyl ethers having one or more alkylether groups, alkylene oxy groups, heteroatom containing aryl groups,heteroatom containing cycloalkyl groups, and the like. Preferred alkylether groups are ethoxy, propoxy, and butoxy. Preferably such compoundscontain from about 1 to about 100 alkyleneoxy groups and more preferablyabout 1 to about 40 alkyleneoxy groups and more preferably from about 1to about 10 alkyleneoxy groups. Preferably the hydrocarbyl groupscomprise C₁₋₁₅ straight or branched chain alkyl, C₂₋₁₅ straight orbranched chain alkenyl, C₅₋₁₈ cycloalkyl, C₆₋₂₄ alkyl substitutedcycloalkyl, C₄₋₁₈ aryl, C₄₋₂₀ aralkyl and C₄₋₂₀ aralkyl groups. Morepreferably the hydrocarbyl groups comprise C₁₋₈ straight or branchedchain alkyl, C₅₋₁₂ cycloalkyl, C₆₋₁₂ alkyl substituted cycloalkyl, C₄₋₁₈aryl, C₄₋₂₀ aralkyl and C₄₋₂₀ alkaryl groups. Preferred alkyl groups areinclude methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, hexyl,ethyl hexyl, with methyl and ethyl even more preferred. Preferredcycloalkyl groups include cyclohexyl and fenchyl. Preferred alkylsubstituted cycloalkene groups include menthyl and isobornyl. Mostpreferred hydrocarbyl groups attached to the carbonyl groups includemethyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, hexyl, ethylhexyl, cyclohexyl, fenchyl, menthyl, phenyl-propyl, furfuryl, phenethyl,adamantyl and isobornyl.

The 1,1-disubstituted alkene compounds can be prepared as disclosed inMalofsky et al., U.S. Pat. Nos. 8,609,885 and 8,884,051; Malofsky et al.WO 2013/059473 and Sullivan et al. U.S. Ser. No. 14/814,961 filed Jul.31, 2015, all incorporated herein by reference in their entirety for allpurposes. In some embodiments the 1,1-disubstituted alkenes are preparedin the form of 1,1-disubstituted alkenes having methyl or ethyl,preferably ethyl, hydrocarbyl groups connected to the carbonyl groups.There after one or more of the hydrocarbyl groups are replaced via theprocess disclosed in Sullivan et al. U.S. Ser. No. 14/814,961 filed Jul.31, 2015. Exemplary 1,1-disubstituted alkene compounds correspond toFormula 1, 2 or 3 as disclosed hereinbefore.

Exemplary hydrocarbyl groups, the presence of which increase the Tg ofpolymers formed therefrom include aryl groups, aralkyl groups, alkarylgroups with the aryl group bonded to the 1 carbon atom, cycloalkylgroups, alkyl groups with a cycloalkyl group on the 1 carbon atom, orbranched alkyl groups wherein the 1 carbon atom is a tertiary or the 1and 2 carbon atoms are secondary. In certain embodiments the hydrocarbylgroups the presence of which increase the Tg of polymers formedtherefrom include a cyclic terpene, alkyl substituted cycloalkyl,adamantyl, furfuryl, tertiary butyl groups, or mixtures thereof. Incertain embodiments, the hydrocarbyl groups, the presence of whichincrease the Tg of polymers formed therefrom include fenchyl, menthyl,cyclohexyl, 2-phenyl propyl, or isobornyl groups. Exemplary1,1-disubstituted alkenes having one or more hydrocarbyl groups on thecarbonyl carbons which increase the glass transition temperatures ofpolymers prepared therefrom are illustrated by Formulas 1 and 2presented hereinbefore. In certain embodiments the substituents on thehydrocarbyl groups on the 1,1-disubstituted alkenes may include alkyl,halo, alkoxy, alkylthio, hydroxyl, nitro, cyano, azido, carboxy,acyloxy, and sulfonyl groups; more preferred substituents include alkyl,halo, alkoxy, alkylthio, and hydroxyl groups, with halo, alkyl andalkoxy are even more preferred. In certain embodiments R¹ is separatelyin each occurrence C₄₋₁₅ branched chain alkyl wherein the 1 carbon atomis a tertiary or the 1 and 2 carbon atoms are secondary, C₄₋₁₅ branchedchain alkenyl wherein the 1 carbon atom is a tertiary or the 1 and 2carbon atoms are secondary, C₅₋₁₈ cycloalkyl, C₆₋₂₄ alkyl substitutedcycloalkyl, C₄₋₁₈ aryl, C₄₋₂₀ aralkyl or C₄₋₂₀ aralkyl groups. Incertain embodiments R¹ is separately in each occurrence C₄₋₈ branchedchain alkyl wherein the 1 carbon atom is a tertiary or the 1 and 2carbon atoms are secondary, C₅₋₁₂ cycloalkyl, C₆₋₁₂ alkyl substitutedcycloalkyl, C₄₋₁₈ aryl, C₄₋₂₀ aralkyl or C₄₋₂₀ alkaryl groups. Incertain embodiments R¹ is separately in each occurrence tertiary butyl,fenchyl, menthyl, cyclohexyl, 2-phenyl propyl, furfuryl, adamantyl andisobornyl.

Preferably R² is separately in each occurrence straight or branchedchain alkyl having a primary 1 carbon atom or a secondary 1 carbon atomand primary 2 carbon atom, straight or branched chain alkenyl having aprimary 1 carbon atom or a secondary 1 carbon atom and primary 2 carbonatom, straight or branched chain alkynyl having a primary 1 carbon atomor a secondary 1 carbon atom and primary 2 carbon atom, cycloalkyl,alkyl substituted cycloalkyl, aryl, aralkyl, or alkaryl, wherein thehydrocarbyl groups may contain one or more heteroatoms in the backboneof the hydrocarbyl group and may be substituted with a substituent thatdoes not negatively impact the ultimate function of the compounds orpolymers prepared from the compounds. In certain embodiments suchsubstituents may include alkyl, halo, alkoxy, alkylthio, hydroxyl,nitro, cyano, azido, carboxy, acyloxy, and sulfonyl groups; morepreferred substituents include alkyl, halo, alkoxy, alkylthio, andhydroxyl groups, with halo, alkyl and alkoxy are even more preferred. Incertain embodiments R² is separately in each occurrence C₁₋₁₅ straightor branched chain alkyl having a primary 1 carbon atom or a secondary 1carbon atom and primary 2 carbon atom, C₂₋₁₅ straight or branched chainalkenyl a primary 1 carbon atom or a secondary 1 carbon atom and primary2 carbon atom, C₅₋₁₈ cycloalkyl, C₆₋₂₄ alkyl substituted cycloalkyl,C₄₋₁₈ aryl, C₄₋₂₀ aralkyl or C₄₋₂₀ alkaryl groups. In certainembodiments R² is separately in each occurrence C₁₋₈ straight orbranched chain alkyl having a primary 1 carbon atom or a secondary 1carbon atom and primary 2 carbon atom, C₅₋₁₂ cycloalkyl, C₆₋₁₂ alkylsubstituted cycloalkyl, C₄₋₁₈ aryl, C₄₋₂₀ aralkyl or C₄₋₂₀ alkarylgroups. In certain embodiments R² is separately in each occurrencemethyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, hexyl, fenchyl,menthyl, cyclohexyl, phenyl propyl or isobornyl. Preferably R′ ishydrogen, alkyl or alkylene group. Preferably R′ is hydrogen or C₁₋₁₀alkyl or alkylene. More preferably R′ is hydrogen of C₁₋₄ alkyl oralkylene. R′ is more preferably hydrogen or C₁₋₄ alkyl. Most preferablyR′ is hydrogen. In the embodiment where R′ is hydrogen the compounds arecommonly referred to a methylene malonates.

In the polymerizable compositions the hydrocarbyl groups that do notincrease the glass transition temperatures of polymers preparedtherefrom, can be any other hydrocarbyl groups. In some embodiments itmay be desirable that such hydrocarbyl groups if homopolymerized,prepare polymers having a glass transition temperature of less than 60°C., preferably between about 30 to about 59° C. Exemplary hydrocarbylgroups that meet these criteria include occurrence alkyl with a primary1 carbon atom or a secondary 1 carbon atom and primary 2 carbon atom,alkenyl with a primary 1 carbon atom or a secondary 1 carbon atom andprimary 2 carbon atom, alkaryl wherein the aryl group is bonded to acarbon atom which is 3 or more carbon atoms from X, alkyl group with acycloalkyl group bonded to a carbon atom which is 3 or more carbon atomsfrom the X, or a polyalkylene ether. In some embodiments suchhydrocarbyl groups include straight chain C₁₋₈ alkyl groups with aprimary 1 carbon atom or a secondary 1 carbon atom and primary 2 carbonatom, straight chain C₁₋₈ alkenyl groups with a primary 1 carbon atom ora secondary 1 carbon atom and primary 2 carbon atom, alkoxy groups,polyalkylene ether groups and the like. In certain embodiments thehydrocarbyl groups may be methyl or ethyl. In formulas 1 to 3 in someembodiments R² is separately in each occurrence alkyl with a primary 1carbon atom or a secondary 1 carbon atom and primary 2 carbon atom,alkenyl with a primary 1 carbon atom or a secondary 1 carbon atom andprimary 2 carbon atom, alkaryl wherein the aryl group is bonded to acarbon atom which is 3 or more carbon atoms from X, alkyl group with acycloalkyl group bonded to a carbon atom which is 3 or more carbon atomsfrom the X, or a polyalkylene ether. In some embodiments R² isseparately in each occurrence straight chain C₁₋₈ alkyl groups with aprimary 1 carbon atom or a secondary 1 carbon atom and primary 2 carbonatom, straight chain C₁₋₈ alkenyl groups with a primary 1 carbon atom ora secondary 1 carbon atom and primary 2 carbon atom, alkoxy groups,polyalkylene ether groups and the like. In some embodiments R² isseparately in each occurrence methyl or ethyl. In some embodiments X isnitrogen, or oxygen sulfur. In some embodiments X is nitrogen, oroxygen. In some embodiments X is oxygen.

The 1,1-disubstituted alkenes can be in the form of diesters, diamides,dithioesters wherein both hydrocarbyl groups are bonded to carbonylgroups through heteroatom, diketones, both hydrocarbyl groups are bondedto carbonyl groups through a direct bond, or keto-esters, ketoamides orketothioesters wherein one hydrocarbyl group is bonded to a carbonylgroup through a heteroatom and the other through a direct bond, ormixtures thereof.

Disclosed are compositions containing the first 1,1-disubstitutedalkenes the presence of which in copolymers of 1,1-disubstitutedalkenes, increase glass transition temperatures of polymers preparedcontaining a primary 1 carbon atom or a secondary 1 carbon atom andprimary 2 carbon atom. In essence the inclusion of the first1,1-disubstituted alkenes in a copolymer increases the glass transitiontemperature of the copolymers formed over the glass transitiontemperatures of polymers and copolymers prepared only from the second1,1-disubstituted alkenes. The hydrocarbyl groups on the carbonylcarbons impact the glass transition temperature (Tg) of polymersprepared from the 1,1-disubstituted 1 alkenes. Tg as used herein can bemeasured using differential scanning calorimetry on a sample of about0.5-20.0 mg. The sample is heated at a rate of about 10° C./min and thencooled at a rate of about 20° C./min. To enhance the Tg a sufficientamount of one or more first 1,1-disubstituted alkenes is included inpolymerizable compostions to increase the glass transition temperaturesof copolymers prepared therefrom. The increase in Tg is compared topolymers or copolymers prepared from the second 1,1-disubstitutedalkenes. Disclosed are compositions which contain the first1,1-disubstituted alkenes and polymers prepared containing the first1,1-disubstituted alkenes. The compositions disclosed herein allow thepreparation of polymerizable compositions and polymers with targetedTg's. By selecting appropriate 1,1-disubstituted alkenes and the amountsthereof the glass transition temperature of polymers prepared therefromcan be controlled. Generally compositions containing 100 percent of oneor more first 1,1-disubstituted alkenes results in polymers with thehighest Tg's. The one or more first 1,1-disubstituted alkenes may haveone or more of the hydrocarbyl groups which increase the resultingpolymers Tg on the carbonyl groups. In monofunctional first1,1-disubstituted alkenes one or both of the hydrocarbyl groups on thecarbonyl carbons which increase the Tg of the resulting polymers may bepresent. In certain embodiments only one of the hydrocarbyl groups onthe carbonyl carbons of the first 1,1-disubstituted alkenes whichincrease the Tg of the resulting polymers may be present as suchcompounds positively impact the Tg of the resulting polymers and suchcompounds are easier to synthesize. Nevertheless compositions disclosedherein may contain monofunctional first 1,1-disubstituted alkenes withboth of the hydrocarbyl groups on the carbonyl carbons which increasethe Tg of the resulting polymers. In multifunctional first1,1-disubstituted alkenes, one or more, up to all, of the hydrocarbylgroups, which increase the Tg of the resulting polymers may be presenton the carbonyl carbons. In some embodiments, the one or more first1,1-disubstituted alkene compounds have at least one hydrocarbyl groupwhich is an aryl group, aralkyl group, alkaryl group with the aryl groupbonded to the 1 or 2 carbon atom, a cycloalkyl group, an alkyl groupwith a cycloalkyl group on the 1 or 2 carbon atom, or a branched alkylgroup wherein the 1 carbon atom is a tertiary or the 1 and 2 carbonatoms are secondary and at least one hydrocarbyl group which is alkylwith a primary 1 carbon atom or a secondary 1 carbon atom and a primary2 carbon atom, alkenyl with a primary 1 carbon atom or a secondary 1carbon atom and a primary 2 carbon atom, alkaryl wherein the aryl groupis bonded to a carbon atom which is 3 or more carbon atoms from thedirect bond or heteroatom, alkyl group with a cycloalkyl group bonded toa carbon atom which is 3 or more carbon atoms from the direct bond orheteroatom, a polyalkylene ether. In some embodiments, the one or morefirst 1,1-disubstituted alkene compounds have at least one hydrocarbylgroup which is an aryl group, aralkyl group, alkaryl group with the arylgroup bonded to the 1 or 2 carbon atom, a cycloalkyl group, an alkylgroup with a cycloalkyl group on the 1 or 2 carbon atom, or a branchedalkyl group wherein the 1 carbon atom is a tertiary or the 1 and 2carbon atoms are secondary and at least one hydrocarbyl group which isC₁₋₈ alkyl with a primary 1 carbon atom or a secondary 1 carbon atom anda primary 2 carbon atom. In some embodiments wherein the first1,1-disubstituted alkene has different hydrocarbyl groups connected tocarbonyl groups, at least one hydrocarbyl group functions to increase Tgas disclosed herein and the other may be a methyl or ethyl group and insome embodiments may be ethyl. The 1,1-disubstituted alkenes can also bemultifunctional having more than one core unit and alkene group. Themultifunctional 1,1-disubstituted alkenes comprise two or more1,1-disubstituted alkene groups linked by the residue of polyfunctionalpolyol which is a polyvalent hydrocarbylene. The polyvalenthydrocarbylene group can be any hydrocarbylene group that can be used inthe preparation of a polyol. The polyvalent hydrocarbylene group caninfluence the glass transition temperature of polymers prepared from1,1-disubstituted alkenes containing such multifunctional 1,1disubstituted-1-alkenes. Such group is also illustrated by R³ in theprevious formulas. Polyvalent hydrocarbylene groups which enhance the Tgof polymers prepared from mixtures containing such multifunctional1,1-disubstruted alkenes include hydrocarbylene groups containing one ormore arylene groups, cycloalkylene groups, aralkyl groups and the like.In certain embodiments such polyvalent hydrocarbylene groups include theresidue of bisphenol A (4,4′-(propane-2,2-diyl) diphenyl), bisphenol F(2,2′-methylenediphenyl), aliphatic polyester polyols, aromaticpolyester polyols, alkane diols, cyclohexyl dimethanol, benzenedimethanol and the like. Exemplary multifunctional 1,1-disubstitutedalkenes are illustrated by Formula 4 disclosed hereinbefore.

In the context of Formula 4, preferably the sum of a and b is 2 to about10 and more preferably 2 to about 5. In exemplary embodiments R³ isseparately in each occurrence straight or branched chain alkylene,straight or branched chain alkenylene, cycloalkylene, alkyl substitutedcycloalkylene, arylene, aralkylene, or alkarylene, wherein thehydrocarbylene groups may contain one or more heteroatoms in thebackbone of the hydrocarbylene group and may be substituted with asubstituent that does not negatively impact the ultimate function of thecompounds or polymers prepared from the compounds. Exemplarysubstituents are those disclosed as useful with respect to R¹. Incertain embodiments R³ is separately in each occurrence C₁₋₁₅ straightor branched chain alkylene, C₂₋₁₅ straight or branched chain alkenylene,C₅₋₁₈ cycloalkylene, C₆₋₂₄ alkyl substituted cycloalkylene, C₄₋₁₈arylene, C₄₋₂₀ aralkylene or C₄₋₂₀ alkarylene groups. In certainembodiments R³ is separately in each occurrence C₁₋₈ straight orbranched chain alkylene, C₅₋₁₂ cycloalkylene, C₆₋₁₂ alkyl substitutedcycloalkylene, C₄₋₁₈ arylene, C₄₋₂₀ aralkylene or C₄₋₂₀ alkarylenegroups.

The presence of multifunctional 1,1-disubstituted alkenes inpolymerizable compositions may function to crosslink polymers preparedtherefrom. Crosslinking may further increase the glass transitiontemperature of the resulting polymers. In some embodiments themultifunctional 1,1-disubstituted alkenes are present in a sufficientamount to increase the glass transition temperature of the resultingpolymers. In some embodiments the multifunctional 1,1-disubstitutedalkenes are present in an amount of about 1 weight percent or greater,more preferably about 5 weight percent or greater and most preferablyabout 15 weight percent or greater. In some embodiments themultifunctional 1,1-disubstituted alkenes may be present in an amount of100 weight percent or less. In some embodiments the multifunctional1,1-disubstituted alkenes may be present in an amount of about 30 weightpercent or less or about 15 weight percent or less. The multifunctional1,1-disubstituted alkenes can be the first multifunctional1,1-disubstituted alkenes, the second 1,1-disubstituted alkenes or amixture thereof. In some embodiments wherein the multifunctional1,1-disubstituted alkenes are present as crosslinkers they are thesecond 1,1-disubstituted alkenes.

The 1,1-disubstituted alkene compounds are preferably prepared using amethod, which results in a sufficiently high purity so that it can bepolymerized. The purity of the 1,1-disubstituted alkene compound may besufficiently high so that 70 mole percent or more, preferably 80 molepercent or more, more preferably 90 mole percent or more, even morepreferably 95 mole percent or more, and most preferably 99 mole percentor more of the 1,1-disubstituted alkene compound is converted to polymerduring a polymerization process. The purity of the 1,1-disubstitutedalkene compound preferably is about 85 mole percent or more, morepreferably about 90 mole percent or more, even more preferably about 93mole percent or more, even more preferably about 95 mole percent ormore, even more preferably about 97 mole percent or more, and mostpreferably about 99 mole percent or more, based on the total moles ofthe 1,1-disubstituted alkene compound. If the 1,1-disubstituted alkenecompound includes the analogous 1,1-disubstituted alkane impurity itshould preferably be about 10 mole percent or less, or more preferablyabout 1 mole percent or less. The concentration of any impuritiescontaining a dioxane group preferably is about 2 mole percent or less,more preferably about 1 mole percent or less, even more preferably about0.2 mole percent or less, and most preferably about 0.05 mole percent orless, based on the total moles of the 1,1-disubstituted alkene compound.The total concentration of any impurity having the alkene group replacedby an analogous hydroxyalkyl group (e.g., by a Michael addition of thealkene with water) preferably is about 3 mole percent or less, morepreferably about 1 mole percent or less, even more preferably about 0.1mole percent or less, and most preferably about 0.01 mole percent orless, based on the total moles in the 1,1-disubstituted alkene compound.Preferred 1,1-disubstituted alkene compounds are prepared by a processincluding one or more (e.g., two or more) steps of distilling a reactionproduct or an intermediate reaction product (e.g., a reaction product orintermediate reaction product of a source of formaldehyde and a malonicacid ester). The 1,1-disubstituted alkenes having the recited puritiespositively impact the glass transition temperature of the polymersprepared therefrom.

The glass transition temperature of compositions containing can bepredicted based on the formula

Tg=Y*W+V±15° wherein

Y is the weight percent of the first 1,1-disubstituted alkene compound;W is the Tg of the first 1,1-disubstituted alkene compound minus the Tgof the second 1,1-disubstituted alkene compound: andV is the Tg of the second 1,1-disubstituted alkene compound;wherein Tg is expressed in ° C. The first 1,1-disubstituted alkenecompound used in any embodiment to enhance the Tg of a copolymer asdisclosed herein must exhibit a Tg of its homopolymer of greater thanthe target Tg. This is important to recognize when utilizing thisformula. A number of other factors can impact the glass transitiontemperature of a polymer prepared from the 1,1-disubstituted alkenes,including molecular weight, amount of multifunctional monomers, amountof impurities present, polydispersity, tacticity and the packing of thepolymer chains. For this reason the actual glass transition that can bedetermined as disclosed herein may be about 15° C. less or greater thanthat predicted by the formula.

The disclosure contained herein provides a way to tailor a polymerizablecomposition or polymer to exhibit a desired glass transitiontemperature. By selection of the first and second 1,1-disubstitutedalkenes, the relative amounts of each and the amount of multifunctional1,1-disubstitued present as a crosslinker a target glass transitiontemperature may be achieved. In general, if from about 5 to about 15weight percent of a multifunctional 1,1-disubstituted alkene is presentthe glass transition temperature is increased from about 10 to about 15°C. This understanding allows the preparation of a number of new monomercompositions and polymers. In some embodiments, the polymerizablecomposition comprises about 10 mole percent or more of one or more first1,1-disubstituted alkene compounds wherein the Tg of the copolymersprepared therefrom is 60° C. or greater. In some embodiments wherein theTg of the copolymers prepared therefrom is 60° C. or greater about 1mole percent or greater, orabout 10 mole percent or greater of one ormore second 1,1-disubstituted alkene compounds may be present. In suchembodiments up to about 90 mole percent of one or more second1,1-disubstituted alkene compounds may be present. In some embodiments,the polymerizable composition comprises about 25 mole percent or more ofthe one or more first 1,1-disubstituted alkene compounds, wherein the Tgof the copolymers prepared therefrom is 80° C. or greater. In someembodiments wherein the Tg of the copolymers prepared therefrom is 80°C. or greater about 1 mole percent or greater, or about 10 mole percentor greater of one or more second 1,1-disubstituted alkene compounds maybe present. In such embodiments up to about 75 mole percent of one ormore second 1,1-disubstituted alkene compounds may be present. In someembodiments, the polymerizable composition comprises about 45 molepercent or more of the one or more first 1,1-disubstituted alkenecompounds wherein the Tg of the copolymers prepared therefrom is 100° C.or greater. In some embodiments wherein the Tg of the copolymersprepared therefrom is 100° C. or greater about 1 mole percent orgreater, or about 10 mole percent or greater of one or more second1,1-disubstituted alkene compounds may be present. In such embodimentsup to about 55 mole percent of one or more second 1,1-disubstitutedalkene compounds may be present. In some embodiments, the polymerizablecomposition, a composition, which comprises about 65 mole percent ormore of the one or more first 1,1-disubstituted alkene compounds whereinthe Tg of the copolymers prepared therefrom is 120° C. or greater. Insome embodiments wherein the Tg of the copolymers prepared therefrom is120° C. or greater about 1 mole percent or greater, or about 10 molepercent or greater of one or more second 1,1-disubstituted alkenecompounds may be present. In such embodiments up to about 35 molepercent of one or more second 1,1-disubstituted alkene compounds may bepresent. Disclosed are new polymers prepared from these compositions.

In some embodiments new polymerizable compositions and polymers preparedtherefrom comprise one or more first 1,1-disubstituted alkene compoundswhich contain one or more hydrocarbyl groups comprising menthyl,fenchyl, isobornyl, furfuryl, cyclohexyl, phenethyl, benzyl, tertiarybutyl, 2-phenyl propyl and, or adamantyl. Homopolymers prepared fromthese first 1,1-disubstituted alkene compounds exhibit high glasstransition temperatures. Compositions containing one or more one or morefirst 1,1-disubstituted alkene compounds which contain one or morehydrocarbyl groups comprising menthyl, fenchyl, isobornyl, furfuryl,cyclohexyl, phenethyl, benzyl, tertiary butyl, 2-phenyl propyl and, oradamantyl and one or more multifunctional 1,1-disubstituted alkenecompounds are disclosed, wherein the one or more multifunctional1,1-disubstituted alkenes can be one or more first multifunctional1,1-disubstituted alkenes, one or more second multifunctional1,1-disubstituted alkenes or mixtures thereof.

Disclosed herein are a number of new compounds comprising one or morefirst 1,1-disubstituted alkene compounds wherein each carbonyl groupindependently has a hydrocarbyl group bonded to the carbonyl groups by adirect bond, or a heteroatom wherein one or more of the hydrocarbylgroups comprise a menthyl, fenchyl, isobornyl, furfuryl, phenethyl,2-phenyl propyl or adamantyl the one or more first 1,1-disubstitutedalkenes correspond to one of formulas 1 or 2

wherein: R¹ is separately in each occurrence a menthyl, fenchyl,isobornyl, furfuryl, phenethyl, 2-phenyl propyl or adamantyl; R², X andR′ are as previously disclosed. Also disclosed are polymers preparedfrom these first 1,1-disubstituted alkenes, homopolymers prepared fromthese first 1,1-disubstituted alkenes, and polymers prepared from thesefirst 1,1-disubstituted alkenes and multifunctional 1,1-disubsitutedalkenes, which may be multifunctional first 1,1-disubsituted alkenes,multifunctional second 1,1-disubsituted alkenes or mixtures thereof.

Disclosed is a method comprising contacting one or more of the first1,1-disubstituted alkene compounds disclosed herein with one or moresecond 1,1-disubstituted alkene compounds disclosed herein with apolymerization initiator under conditions to polymerize the compositionand the glass transition temperature of the resulting polymer isincreased over the glass transition temperature of a homopolymer of theone or more second 1,1-disubstituted alkene compounds. In someembodiments about 10 mole percent or greater of the first1,1-disubstituted alkene compounds is present. This method can beutilized with any composition disclosed herein.

The polymerizable compositions disclosed herein can be polymerized byexposing the composition to free radical polymerization conditions or toanionic polymerization conditions. Free radical polymerizationconditions are well known to those skilled in the art such as disclosedin U.S. Pat. No. 6,458,956 incorporated herein by reference. In certainembodiments the polymerizable compositions are exposed to anionicpolymerization conditions. The polymerizable compositions are contactedwith any anionic polymerization initiator or with any nucleophilicmaterial. As the 1,1-disubstitued alkenes are highly electrophiliccontact with any nucleophilic material can initiate anionicpolymerization. Anionic polymerization is commonly referred to as livingpolymerization because the terminal portion of the polymeric chains arenucleophilic and will react with any unreacted 1,1-disubstituted alkenesthey come into contact with. Thus the polymerizable composition willcontinue until all available unreacted 1,1-disubstitued alkenespolymerize or the polymerizing mixture is subjected to a quenching step.In a quenching step the mixture is contacted with an acid whichterminates the polymeric chain ends and stops further polymerization.The polymerization can proceed at any reasonable temperature includingat ambient temperatures, from about 20 to 35° C., depending on ambientconditions. The polymerization can be performed in bulk, without asolvent or dispersant, or in a solvent or dispersant.

According to certain embodiments, a suitable polymerization initiatorcan generally be selected from any agent that can initiatepolymerization substantially upon contact with a selected polymerizablecomposition. In certain embodiments, it can be advantageous to selectpolymerization initiators that can induce polymerization under ambientconditions and without requiring external energy from heat or radiation.In embodiments wherein the polymerizable composition comprises one ormore 1,1-disubstituted alkene compounds, a wide variety ofpolymerization initiators can be utilized including most nucleophilicinitiators capable of initiating anionic polymerization. Exemplaryinitiators include alkali metal salts, alkaline earth metal salts,ammonium salts, amines, halides (halogen containing salts), metaloxides, and mixtures containing such salts or oxides. Exemplary anionsfor such salts include anions based on halogens, acetates, benzoates,sulfur, carbonates, silicates and the like. The mixtures containing suchcompounds can be naturally occurring or synthetic. Specific examples ofexemplary polymerization initiators for 1,1-disubstituted alkenecompounds can include glass beads (being an amalgam of various oxidesincluding silicon dioxide, sodium oxide, and calcium oxide), ceramicbeads (comprised of various metals, nonmetals and metalloid materials),clay minerals (including hectorite clay and bentonite clay), and ioniccompounds such as sodium silicate, sodium benzoate, and calciumcarbonate. Other polymerization initiators can also be suitableincluding certain plastics (e.g., ABS, acrylic, and polycarbonateplastics) and glass-fiber impregnated plastics. Additional suitablepolymerization initiators for such polymerizable compositions are alsodisclosed in U.S. Patent App. Publication No. 2015/0073110, which ishereby incorporated by reference. In some embodiments the polymerizationinitiator may be encapsulated using any encapsulation method compatiblewith the polymerization of the 1,1-disubstituted alkenes. In someembodiments the encapsulated initiator (activation agent) may be asdisclosed in Stevenson et al. Ser. No. 14/725,532 filed May 29, 2015incorporated herein by reference in its entirety for all purposes.

Polymerization can be terminated by contacting the polymeric mixturewith an anionic polymerization terminator. In some embodiments theanionic polymerization terminator is an acid. In some embodiments it isdesirable to utilize a sufficient amount of the acid to render thepolymerization mixture slightly acidic, preferably having a pH of lessthan 7, more preferably less than about 6. Exemplary anionicpolymerization terminators include, for example, mineral acids such asmethane sulfonic acid, sulfuric acid, and phosphoric acid and carboxylicacids such as acetic acid and trifluoroacetic acid.

The polymerizable compositions may be polymerized in bulk, which is inthe absence of a solvent or dispersant, in a solution or in an emulsion.Polymerization in bulk can be performed by contacting the polymerizablecomposition which may include any of the other ingredients disclosedherein with a suitable substrate and an activator and allowing thecomposition to polymerize.

The polymerizable compositions may be prepared by emulsionpolymerization. For example the polymerizable compositions may beprepared by the process disclosed in Stevenson et al., U.S. Ser. No.14/789,178 filed Jul. 1, 2015 incorporated herein by reference in itsentirely for all purposes. Disclosed in Stevenson et al., is a processcomprising the steps of: agitating a mixture including: about 25 weightpercent or more of a carrier liquid, a surfactant (e.g., an emulsifier)and one or more monomers to form micelles of the one or more monomers inthe carrier liquid, wherein the one or more monomers includes one ormore 1,1-disubstituted alkenes; reacting an activator with at least oneof the monomers in the micelle for initiating the anionic polymerizationof the one or more monomers; and anionically polymerizing the one ormore monomers. The polymerization process preferably includes one ormore surfactants for forming an emulsion having micelles or a discretephase including a monomer (e.g., a 1,1-disubstituted alkene compound)distributed throughout a continuous phase (e.g., a continuous phaseincluding a carrier liquid). The surfactant may be an emulsifier, adefoamer, or a wetting agent. The surfactant preferably is present in asufficient quantity so that a stable emulsion is formed by mixing orotherwise agitating a system including the monomer and carrier liquid.The surfactants according to the teachings herein include one or moresurfactants for improving the stability of emulsion (i.e., for improvingthe stability of the dispersed phase in the carrier liquid phase). Thesurfactant and/or the amount of surfactant is preferably selected sothat all of the monomer micelles are covered by a layer of thesurfactant. The surfactant may include an amphoteric surfactant, anonionic surfactant, or any combination thereof. The surfactantpreferably is free of anionic surfactants during the polymerizationprocess. One example of a preferred surfactant (e.g., an emulsifier) isan ethoxylate, such as an ethoxylated diol. For example, the surfactantmay include 2,4,7,9-tetramethyl-5-decyne-4,7-diol ethoxylate. Thesurfactant may include a poly(alkene glycol). Another example of apreferred surfactant is a poly(ethylene glycol)-block-poly(propyleneglycol)-block-poly(ethylene glycol) copolymer. Another example of apreferred surfactant is a surfactant including an alcohol, anethoxylated alcohol, or both. For example, the surfactant may includeCARBOWET® 138 nonionic surfactant (including alkyl alcohol, polyethyleneglycol, ethoxylated C9-C11 alcohols). Another example of a preferredsurfactant is a surfactant including a sorbitan, a sorbitol, or apolyoxyalkene. For example, the surfactant may include sorbitanmonopalmitate (nonionic surfactant). Other examples of preferredsurfactants include branched polyoxyethylene (12) nonylphynyl ether(IGEPAL® CO-720) and poly(ethylene glycol) sorbitol hexaoleate (PEGSH).The amount of the surfactant (e.g., the amount of the emulsifier)preferably is sufficient to form a layer that substantially encapsulatesthe monomer and subsequent polymer particles. The amount of surfactantpreferably is sufficient so that the discrete phase has a diameter ofabout 10 mm or less, about 1 mm or less, about 300 μm or less, or about100 μm or less. The amount of the surfactant is preferably sufficient sothat the discrete phase has a diameter of about 0.01 μm or more, about0.1 μm or more, about 1 μm or more, about 10 μm or more, or about 50 μmor more. The concentration of the surfactant may be about 0.001 weightpercent or more, preferably about 0.01 weight percent or more, morepreferably about 0.1 weight percent or more, and most preferably about0.5 weight percent or more, based on the total weight of the emulsion.The concentration of the surfactant may be about 15 weight percent orless, preferably about 10 weight percent or less, and more preferablyabout 6 weight percent or less, and most preferably about 3 weightpercent or less, based on the total weight of the emulsion. The weightratio of the surfactant to the total weight of the monomer and polymerin the emulsion (e.g., at the end of the polymerization process)preferably is about 0.0001 or more, more preferably about 0.002 or more,even more preferably about 0.005 or more, and most preferably about 0.01or more. The weight ratio of the surfactant to the total weight of themonomer and polymer in the emulsion (e.g., at the end of thepolymerization process) preferably is about 5 or less (i.e., about 5:1or less), more preferably about 1 or less, even more preferably about0.5 or less, and most preferably about 0.1 or less. The carrier liquidis preferably water. The polymerization process may include a step ofapplying shear forces or sonication to a mixture including at least thesurfactant and the carrier fluid for forming an emulsion. For example,the process may include stirring or otherwise agitating the mixture forcreating the emulsion.

The polymerizable compositions disclosed herein may be polymerized insolution via anionic polymerization processes. In some embodiments thepolymerizable compositions may be polymerized utilizing the methoddisclosed in Palsule et al. U.S. Ser. No. 14/810,741 filed Jul. 28,2015, incorporated herein in its entirety for all purposes. According tothe process disclosed in Palsule et al. the process comprises the stepsof mixing one or more 1,1-disubstituted alkenes and a solvent; adding anactivator; reacting the activator with the one or more 1,1-disubstitutedalkenes to initiate the anionic polymerization of the one or more1,1-disubstituted alkenes; and anionically polymerizing the one or more1,1-disubstituted alkenes to form a polymer. The concentration of themonomer in the solution polymerization process may be sufficiently lowso that after polymerization, the solution can flow. If theconcentration of the monomer is too high, the solution becomes tooviscous at the end of the polymerization process and the solution may bedifficult to handle. The concentration of the monomer in the solutionpolymerization process may be sufficiently high so that thepolymerization process is economical. The one or more monomers ispreferably present at a concentration of about 0.5 weight percent ormore, more preferably about 2 weight percent or more, even morepreferably about 5 weight percent or more, and most preferably about 8weight percent or more, based on the total weight of the solvent andmonomer. The one or more monomers may be present at a concentration ofabout 90 weight percent or less, preferably about 75 weight percent orless, more preferably about 50 weight percent or less, even morepreferably about 30 weight percent or less, and most preferably about 20weight percent or less. If the monomer is added at multiple times (suchas continuous and/or sequential monomer addition), it will beappreciated that the amount of the one or more monomers refers to thetotal amount of monomer and polymer and by-products of the monomer thatare present when the addition of monomer has been completed. Thepolymerization process includes one or more solvents selected so thatthe monomer and solvent form a single phase. Preferably the solvent doesnot chemically react with the other components of the solutionpolymerization system during the polymerization process. For example,the solvent preferably does not react with the monomer. As anotherexample, the solvent preferably does not react with the activator.Preferred solvents are organic solvents, or mixtures of organicsolvents. Such solvents, or solvent mixtures typically are in a liquidstate at the reaction temperature(s) (e.g., during activation and/orduring polymerization. The pressure of the solvent (e.g., organicsolvent) and of the monomer at the polymerization temperature should besufficiently low so that the risk of the reactor failing fromover-pressure is reduced or eliminated. For example the partial pressureof the solvent, of the monomer, or both, at the polymerizationtemperature may be about 500 Torr or less, about 200 Torr or less, about50 Torr or less, or about 5 Torr or less. It may be desirable for thesolvent to be substantially or entirely free of any solvent that mayreact with the monomer via Michael addition. However, by selectingreaction conditions so that the polymerization reaction is sufficientlyfast, it may be possible to employ such monomers in the solventpolymerization process. For example, by selecting parameters such asmonomer feed rates, reaction temperature, monomer type, and pH, it maybe possible to employ a solvent including or consisting of a proticsolvent, such as an alcohol. The solution polymerization may beinitiated using an activator capable of initiating anionicpolymerization of the 1,1-disubstituted alkene containing compound. Thesolvent and/or one or more of the monomers (e.g., the 1,1-disubstitutedalkene compounds) may further contain other components to stabilize themonomer prior to exposure to polymerization conditions or to adjust theproperties of the final polymer for the desired use. Prior to thepolymerization reaction, one or more inhibitors may be added to reduceor prevent reaction of the monomer. Such inhibitors may be effective inpreventing anionic polymerization of the monomer, free radicalpolymerization of the monomer, reaction between the monomer and othermolecules (such as water), or any combination thereof.

The polymerization processes disclosed may include a step of applyingshear forces to a mixture including at least the monomer and the solventor carrier. For example, the process may include stirring or otherwiseagitating the mixture for creating the solution or emulsion, fordispersing or removing a precipitated polymer, for controlling thermalgradients, or any combination thereof. The polymerization processespreferably include a reaction temperature at which the partial pressureof the solvent is generally low. For example, the partial pressure ofthe solvent and/or the monomer may be about 400 Torr or less, about 200Torr or less, about 100 Torr or less, about 55 Torr or less, or about 10Torr or less. The reaction temperature preferably is about 80° C. orless, more preferably about 70° C. or less, even more preferably about60° C. or less, even more preferably about 55° C. or less, even morepreferably about 45° C. or less, even more preferably about 40° C. orless, and most preferably about 30° C. or less. The reaction temperaturetypically is sufficiently high that the solvent or carrier liquid andthe monomer are in a liquid state. For example, the reaction temperaturemay be about −100° C. or more, about −80° C. or more, about −30° C. ormore, or about 10° C. or more. When polymerizing a 1,1-disubstitutedalkene compound, it may be desirable to add one or more acid compoundsto the solution, to the monomer, or both, so that the initial pH of thesolution is about 7 or less, about 6.8 or less, about 6.6 or less, orabout 6.4 or less. The polymerization process may be stopped prior tothe completion of the polymerization reaction or may be continued untilthe completion of the polymerization reaction. Preferably, the reactionrate is sufficiently high and/or the reaction time is sufficiently longso that the polymerization reaction is substantially complete.

The conversion of the monomer to polymer may be about 30 weight percentor more, about 60 weight percent or more, about 90 weight percent ormore, about 95 weight percent or more, or about 99 weight percent ormore. The conversion of monomer to polymer may be about 100 weightpercent or less.

The polymerizable compositions may further contain other components tostabilize the compositions prior to exposure to polymerizationconditions or to adjust the properties of the final polymer for thedesired use. For example, in certain embodiments, a suitable plasticizercan be included with a reactive composition. Exemplary plasticizers arethose used to modify the rheological properties of adhesive systemsincluding, for example, straight and branched chain alkyl-phthalatessuch as diisononyl phthalate, dioctyl phthalate, and dibutyl phthalate,trioctyl phosphate, epoxy plasticizers, toluene-sulfamide,chloroparaffins, adipic acid esters, sebacates such as dimethylsebacate, castor oil, xylene, 1-methyl-2-pyrrolidone and toluene.Commercial plasticizers such as HB-40 partially hydrogenated terpenemanufactured by Solutia Inc. (St. Louis, Mo.) can also be suitable.

For example, one or more dyes, pigments, toughening agents, impactmodifiers, rheology modifiers, natural or synthetic rubbers, filleragents, reinforcing agents, thickening agents, opacifiers, inhibitors,fluorescence markers, thermal degradation reducers, thermal resistanceconferring agents, surfactants, wetting agents, or stabilizers can beincluded in a polymerizable system. For example, thickening agents andplasticizers such as vinyl chloride terpolymer (comprising vinylchloride, vinyl acetate, and dicarboxylic acid at various weightpercentages) and dimethyl sebacate respectively, can be used to modifythe viscosity, elasticity, and robustness of a system. In certainembodiments, such thickening agents and other compounds can be used toincrease the viscosity of a polymerizable system from about 1 to 3 cPsto about 30,000 cPs, or more.

According to certain embodiments, stabilizers can be included in thepolymerizable compositions to increase and improve the shelf life and toprevent spontaneous polymerization. Generally, one or more anionicpolymerization stabilizers and or free-radical stabilizers may be addedto the compositions. Anionic polymerization stabilizers are generallyelectrophilic compounds that scavenge bases and nucleophiles from thecomposition or growing polymer chain. The use of anionic polymerizationstabilizers can terminate additional polymer chain propagation.Exemplary anionic polymerization stabilizers are acids, exemplary acidsare carboxylic acids, sulfonic acids, phosphoric acids and the like.Exemplary stabilizers include liquid phase stabilizers (e.g.,methanesulfonic acid (“MSA”)), and vapor phase stabilizers (e.g.,trifluoroacetic acid (“TFA”)). Free-radical stabilizers preferablyinclude phenolic compounds (e.g., 4-methoxyphenol or mono methyl etherof hydroquinone (“MeHQ”) and butylated hydroxy toluene (BHT)).Stabilizer packages for 1,1-disubstituted alkenes are disclosed in U.S.Pat. No. 8,609,885 and U.S. Pat. No. 8,884,051, each incorporated byreference. Additional free radical polymerization inhibitors aredisclosed in U.S. Pat. No. 6,458,956 and are hereby incorporated byreference. Generally, only minimal quantities of a stabilizer are neededand, in certain embodiments only about 150 parts-per-million or less canbe included. In certain embodiments, a blend of multiple stabilizers canbe included such as, for example a blend of anionic stabilizers (MSA)and free radical stabilizers (MeHQ). The one or more anionicpolymerization stabilizers are present in sufficient amount to preventpremature polymerization. Preferably, the anionic polymerizationstabilizers are present in an amount of about 0.1 part per million orgreater based on the weight of the composition, more preferably about 1part per million by weight or greater and most preferably about 5 partsper million by weight or greater. Preferably, the anionic polymerizationstabilizers are present in an amount of about 1000 parts per million byweight or less based on the weight of the composition, more preferablyabout 500 parts per million by weight or less and most preferably about100 parts per million by weight or less. The one or more free radicalstabilizers are present in sufficient amount to prevent prematurepolymerization. Preferably, the free radical polymerization stabilizersare present in an amount of about 1 parts per million or greater basedon the weight of the composition, more preferably about 5 parts permillion by weight or greater and most preferably about 10 parts permillion by weight or greater. Preferably, the free radicalpolymerization stabilizers are present in an amount of about 5000 partsper million by weight or less based on the weight of the composition,more preferably about 1000 parts per million by weight or less and mostpreferably about 500 parts per million by weight or less.

The polymerizable compositions and polymers disclosed herein may beutilized and a number of applications. Exemplary applications includeadhesives, sealants, coatings, components for optical fibers, pottingand encapsulating materials for electronics, resins and pre-polymers asraw materials in other systems, and the like.

The polymerizable compositions exhibit a number of advantageousproperties including rapid reactivity, room or low temperaturereactivity, tailorable rheological characteristics, and the like.Polymers prepared from the polymerizable compositions exhibit a numberof advantageous properties including for example, high glass transitiontemperature, high degradation temperature, high heat resistance, highstiffness and modulus, good rigidity and the like.

Other components commonly used in curable compositions may be used inthe compositions of this invention. Such materials are well known tothose skilled in the art and may include ultraviolet stabilizers andantioxidants and the like. The compositions of the invention may alsocontain durability stabilizers known in the art. Among preferreddurability stabilizers are alkyl substituted phenols, phosphites,sebacates and cinnamates.

ILLUSTRATIVE EMBODIMENTS

The following examples are provided to illustrate the invention, but arenot intended to limit the scope thereof. All parts and percentages areby weight unless otherwise indicated.

Polymerization Process

A number of polymerizable compositions are polymerized according to thefollowing procedure. Tetrahydrofuran (THF) (9.0 g) and methylenemalonate monomers (1.0 g) are charged into a round bottom flask or HDPEbottle. Typically a 10% polymer solution is desired, if 100% conversionof the monomer is to be achieved. Other ratios may be used as desired. Amagnetic stirring bar of appropriate size was added into the flask andthe mixture is allowed to stir on a magnetic stirring plate for 5minutes. A 1% solution of tetramethyl guanidine (TMG) in THF, is chargedinto the flask containing monomer solution under agitation. The amountof activator can represent 1:1000 mole ratio of activator to monomer.Other ratios may be used depending on the speed of reaction desired andmolecular weights of the final polymers. The reaction is continued atroom temperature for 1 hour. For higher monomer/polymer concentrations(above 10 wt % in solvent) or high molecular weight build-ups, viscosityof the solution visibly increases as molecular weight builds up. Samplesare removed for characterization (e.g. GPC) at appropriate timeintervals, if molecular weight increase is monitored as an indication ofthe progress of polymerization. Upon completion of polymerization, a fewdrops of TFA are added to the solution to quench the reaction. Theresulting solution is precipitated into methanol. The precipitate isdried in a vacuum oven at room temperature. The desired polymer isobtained as a white powder.

The polymerization of EBA keto ester monomer is performed in bulk byaddition of 1:100 ratio of TMG initiator to monomer in an aluminum panwith no agitation. Polymerization proceeds until the further growth inmolecular weight is not possible due to gelation. Polymer isprecipitated in methanol and allowed to dry in a vacuum oven withoutusing heat. The subsequent polymer, relatively clean of low molecularweight oligomers and impurities is used for GPC and DSC analysis.

The 1,1-disubstituted alkenes of the polymerizable compositions and theglass transition temperature of the polymers prepared by the disclosedprocess are shown in Table 1. Glass transition temperatures aredetermined by DSC plots using a Differential Scanning calorimeter, Q2000by TA Instruments using a 10° C./minute heating rate. Decompositionprofiles were obtained using a Thermogravimetric Analyzer (TGA), Model Q50 by TA Instruments using a 10° C./minute heating rate.

TABLE 1 Glass transition temperatures 1,1-disubstituted alkenes ° C.Fenchyl methyl methylene malonate (F3M), 100% 151-190 Fenchyl ethylmethylene malonate (FEMM), 100% 150-175 Menthyl ethyl methylene malonate(MEMM), 100% 135-145 Phenyl propyl ethyl methylene malonate (PEMM), 100%61 Phenyl propyl methyl methylene malonate, (P3M), 100% 65 Dicyclohexylmethylene malonate (DCHMM), 100% 140 Ethyl 2-benzoylacrylate (EBA ketoester) 99 75% F3M + 25% DEMM 137 50% F3M + 50% DEMM 95 25% F3M + 75%DEMM 58

FIG. 1 is a DSC trace of the polymer based on fenchyl ethyl methylenemalonate (FEMM) which shows the glass transition temperature as 175° C.FIG. 2 is a TGA trace of FEMM which shows a decomposition temperature of238° C. for 95% weight loss. The number average molecular weight of thispolymer is 293K and weight average molecular weight is 888K. FIG. 3 is aDSC trace of phenyl propyl ethyl methylene malonate (PEMM) which shows aTg of 62° C. FIG. 4 is a TGA trace of PEMM which shows a decompositiontemperature of 284° C. for 95% weight loss. The number average molecularweight of this polymer is 74.5K and weight average molecular weight is450K.

The polymer made from EBA keto ester monomer exhibits a number averagemolecular weight of 14,000 and weight average molecular weight of32,000K. DSC trace of this polymer shows a Tg of 99° C.

Random copolymers of DEMM and F3M are prepared varying the amount ofDEMM and F3M in the feed. FIG. 6 shows the Tg's of 3 random copolymerswith varying amounts of DEMM and F3M in the feed. The Tg of thecopolymer shifts towards the Tg of the homopolymer depending on whichpolymer is present in excess in the feed. For a 50:50 ratio of the twomonomers in the feed, the Tg of the copolymer is roughly in the middleof the range of the two homopolymer Tgs.

The improvement in mechanical properties of the compositions with theaddition of the monomer promoting the formation of polymers with high Tgis confirmed by conducting tensile shear testing. On cold rolled steelpanels, an initiator solution of 0.1 wt % sodium pyruvate in ethanol.After the solvent is flashed off the surface of the panel is primed foranionic polymerization. 100% DEMM, 100% FEMM, 50:50 DEMM+FEMM and 75:25FEMM+DEMM monomers are then applied to the pre-initiated steel surfacesallowing them to polymerize anionically forming an adhesive joint. Thesurfaces are allowed to cure for 72 hours at room temperature. Theresults of the tensile shear bond strength after complete cure can besummarized in Table 2 below.

1,1 disubstituted alkene monomer of blends Tensile shear strength (MPa)DEMM 4.8 FEMM 5.9 50% DEMM and 50% FEMM 10.3 25% DEMM and 75% FEMM 14.4The tensile shear strength obtained by blending or copolymerizing thetwo monomers is much higher than the tensile shear strength obtainedwith the two homopolymers alone.

These results illustrate that incorporation of groups such as fenchyl,menthyl, 2-phenyl propyl, dicyclohexyl etc. enhance the glass transitiontemperatures (Tg) of the polymer composition in comparison to diethylmethylene malonate (Tg=30° C.) or dimethyl methylene malonate (Tg=55°C.). Also performance synergies can be obtained by copolymerizing amonomer capable of producing a high Tg polymer with low Tg monomers suchas DEMM resulting in improved mechanical properties.

Parts by weight as used herein refers to 100 parts by weight of thecomposition specifically referred to. Any numerical values recited inthe above application include all values from the lower value to theupper value in increments of one unit provided that there is aseparation of at least 2 units between any lower value and any highervalue. As an example, if it is stated that the amount of a component ora value of a process variable such as, for example, temperature,pressure, time and the like is, for example, from 1 to 90, preferablyfrom 20 to 80, more preferably from 30 to 70, it is intended that valuessuch as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. are expresslyenumerated in this specification. For values which are less than one,one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate.These are only examples of what is specifically intended and allpossible combinations of numerical values between the lowest value, andthe highest value enumerated are to be considered to be expressly statedin this application in a similar manner. Unless otherwise stated, allranges include both endpoints and all numbers between the endpoints. Theuse of “about” or “approximately” in connection with a range applies toboth ends of the range. Thus, “about 20 to 30” is intended to cover“about 20 to about 30”, inclusive of at least the specified endpoints.The term “consisting essentially of” to describe a combination shallinclude the elements, ingredients, components or steps identified, andsuch other elements ingredients, components or steps that do notmaterially affect the basic and novel characteristics of thecombination. The use of the terms “comprising” or “including” todescribe combinations of elements, ingredients, components or stepsherein also contemplates embodiments that consist essentially of theelements, ingredients, components or steps. Plural elements,ingredients, components or steps can be provided by a single integratedelement, ingredient, component or step. Alternatively, a singleintegrated element, ingredient, component or step might be divided intoseparate plural elements, ingredients, components or steps. Thedisclosure of “a” or “one” to describe an element, ingredient, componentor step is not intended to foreclose additional elements, ingredients,components or steps.

What is claimed is:
 1. A composition comprising one or more1,1-dicarbonylsubstituted alkene compounds wherein each carbonyl groupindependently has a hydrocarbyl group bonded to the carbonyl groups by adirect bond, a heteroatom, and the hydrocarbyl groups are selected suchthat homopolymers prepared from the 1,1-disubstituted alkenes exhibitglass transition temperatures of less than 60° C. and one or more: andone or more multifunctional 1,1-dicarbonylsubstituted alkene compoundswhich comprise a core unit of two or more 1,1-dicarbonylsubstitutedalkenes which correspond to the formula:

wherein: R¹ is separately in each occurrence a hydrocarbyl groupcomprising an aryl group, aralkyl group, alkaryl group with the arylgroup bonded to the 1 or 2 carbon atom, a cycloalkyl group, an alkylgroup with a cycloalkyl group on the 1 or 2 carbon atom, or a branchedalkyl group wherein the 1 carbon atom is a tertiary or the 1 and 2carbon atoms are secondary; R² is, separately in each occurrence, alkylwith a primary 1 carbon atom or a secondary 1 carbon atom and a primarysecond carbon atom, alkenyl with a primary 1 carbon atom or a secondary1 carbon atom and a primary second carbon atom, alkaryl wherein the arylgroup is bonded to a carbon atom which is 3 or more carbon atoms from X,alkyl group with a cycloalkyl group bonded to a carbon atom which is 3or more carbon atoms from the X, a polyalkylene or ether; R³ isseparately in each occurrence a polyvalent hydrocarbon group; R′ isseparately in each occurrence hydrocarbyl or hydrogen; X is a heteroatomor a direct bond; a is separately in each occurrence an integer of 1 ormore; b is separately in each occurrence an integer of 0 or more whereinthe sum or a and b is 2 or greater and the number of valences of R³ isequal to the sum of a and b; wherein the one or more multifunctional1,1-dicarbonylsubstituted alkene compounds are present in sufficientamount to increase the glass transition temperatures of polymersprepared from the composition.
 2. A composition according to claim 1wherein the 1,1-dicarbonylsubstituted alkenes have hydrocarbyl groups ofalkyl with a primary 1 carbon atom or a secondary 1 carbon atom andprimary 2 carbon atom, alkenyl with a primary 1 carbon atom or asecondary 1 carbon atom and primary 2 carbon atom, alkaryl wherein thearyl group is bonded to a carbon atom which is 3 or more carbon atomsfrom the direct bond, oxygen atom, nitrogen atom or sulfur atom, alkylgroup with a cycloalkyl group bonded to a carbon atom which is 3 or morecarbon atoms from the direct bond, oxygen atom, nitrogen atom or sulfuratom, or a polyalkylene ether.
 3. A composition according to claim 1wherein the one or more second 1,1-disubstituted alkenes correspond toformula 3

wherein: R² is, separately in each occurrence a hydrocarbyl groupselected such that homopolymers prepared having the selected hydrocarbylgroups exhibit glass transition temperatures of less than 60° C.; R′ isseparately in each occurrence hydrocarbyl or hydrogen and X is aheteroatom or a direct bond.
 4. A composition according to claim 3wherein R² is separately in each occurrence alkyl with a primary 1carbon atom or a secondary 1 carbon atom and primary 2 carbon atom,alkenyl with a primary 1 carbon atom or a secondary 1 carbon atom andprimary 2 carbon atom, alkaryl wherein the aryl group is bonded to acarbon atom which is 3 or more carbon atoms from X, alkyl group with acycloalkyl group bonded to a carbon atom which is 3 or more carbon atomsfrom the X, or a polyalkylene ether.
 5. A composition according to claim1 wherein the one or more 1,1-dicarbonylsubstituted alkene compoundsexhibit a purity of 95 mole percent or greater, have one mole percent orless of the analogous 1,1-disubstituted alkane, 1 mole percent or lessof an impurity containing a dioxane group, about 1 mole percent of lessof any impurity having the alkene group replaced by an analogoushydroxyalkyl group wherein mole percent is based on the total moles inthe 1,1-dicarbonylsubstituted alkene compound.
 6. A compositionaccording to claim 1 wherein the one or more multifunctional1,1-dicarbonylsubstituted alkene compounds are present in an amount ofabout 1 weight percent or greater to less than 100 weight percent.
 7. Acomposition according to claim 1 wherein the one or more multifunctional1,1-dicarbonylsubstituted alkene compounds are present in an amount ofabout 5 weight percent or greater about 30 weight percent or less.
 8. Acomposition according to claim 1 wherein the Tg of the polymers preparedtherefrom is 60° C. or greater.
 9. A composition according to claim 1wherein the Tg of the copolymers prepared therefrom is 80° C. orgreater.
 10. A composition comprising a copolymer prepared from acomposition of claim
 1. 11. A composition comprising a copolymerprepared from a composition of claim 1 having a glass transitiontemperature of 60° C. or greater.
 12. A composition according to claim11 wherein the 1,1-dicarbonylsubstituted alkenes have hydrocarbyl groupsof alkyl with a primary 1 carbon atom or a secondary 1 carbon atom andprimary 2 carbon atom, alkenyl with a primary 1 carbon atom or asecondary 1 carbon atom and primary 2 carbon atom, alkaryl wherein thearyl group is bonded to a carbon atom which is 3 or more carbon atomsfrom the direct bond, oxygen atom, nitrogen atom or sulfur atom, alkylgroup with a cycloalkyl group bonded to a carbon atom which is 3 or morecarbon atoms from the direct bond, oxygen atom, nitrogen atom or sulfuratom, or a polyalkylene ether.
 13. A composition according to claim 11wherein the one or more second 1,1-disubstituted alkenes correspond toformula 3

wherein: R² is, separately in each occurrence a hydrocarbyl groupselected such that homopolymers prepared having the selected hydrocarbylgroups exhibit glass transition temperatures of less than 60° C.; R′ isseparately in each occurrence hydrocarbyl or hydrogen and X is aheteroatom or a direct bond.
 14. A composition according to claim 13wherein R² is separately in each occurrence alkyl with a primary 1carbon atom or a secondary 1 carbon atom and primary 2 carbon atom,alkenyl with a primary 1 carbon atom or a secondary 1 carbon atom andprimary 2 carbon atom, alkaryl wherein the aryl group is bonded to acarbon atom which is 3 or more carbon atoms from X, alkyl group with acycloalkyl group bonded to a carbon atom which is 3 or more carbon atomsfrom the X, or a polyalkylene ether.
 15. A composition according toclaim 11 wherein the one or more 1,1-dicarbonylsubstituted alkenecompounds exhibit a purity of 95 mole percent or greater, have one molepercent or less of the analogous 1,1-disubstituted alkane, 1 molepercent or less of an impurity containing a dioxane group, about 1 molepercent of less of any impurity having the alkene group replaced by ananalogous hydroxyalkyl group wherein mole percent is based on the totalmoles in the 1,1-dicarbonylsubstituted alkene compound.
 16. Acomposition according to claim 11 wherein the one or moremultifunctional 1,1-dicarbonylsubstituted alkene compounds are presentin an amount of about 1 weight percent or greater to less than 100weight percent.
 17. A composition according to claim 11 wherein the oneor more multifunctional 1,1-dicarbonylsubstituted alkene compounds arepresent in an amount of about 5 weight percent or greater about 30weight percent or less.
 18. A composition according to claim 11 whereinthe polymers exhibit a weight average molecular weight of about 2000 toabout 3,000,000 daltons and a polydispersity of about 1.01 to 10 asdetermined Gel Permeation Chromatography.
 19. A method comprisingcontacting one or more of the 1,1-dicarbonylsubstituted alkene compoundswith one or more of the multifunctional 1,1-dicarbonylsubstituted alkenecompounds according to claim 1 with a polymerization initiator underconditions to polymerize the composition and the glass transitiontemperature of the resulting polymer is increased over the glasstransition temperature of a homopolymer of the one or more1,1-disubstituted alkene compounds.
 20. A method according to claim 19wherein the one or more multifunctional 1,1-dicarbonylsubstituted alkenecompounds are present in an amount of about 1 weight percent or greaterto less than 100 weight percent.